JPH0692687A - Crystallized glass composition containing needle-like dielectric material particle - Google Patents

Abstract

PURPOSE:To provide a crystallized glass composition suitable for wiring board for a high-frequency integrated circuit (MIC) and various multi-layer substrates (dielectric material layer), simultaneously satisfying excellent electric characteristics such as dielectric characteristics and mechanical characteristics, containing needle-like dielectric material particles. CONSTITUTION:Needle-like dielectric material particles having >=15 dielectric constant and >=3 aspect ratio are blended with a glass composition which is moldable into a desired shape at a low temperature and has excellent characteristics in terms of weather resistance and production such as productivity and burnt to give the objective crystallized glass composition simultaneously satisfying excellent electric characteristics such as dielectric characteristics and mechanical characteristics in a frequency band used. The crystallized glass composition is especialy suitable for wiring board for a high-frequency integrated circuit (MIC) and various multi-layer substrates (dielectric material layer).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallized glass composition containing acicular dielectric particles, and particularly to a high frequency integrated circuit (MI
The present invention relates to a crystallized glass composition suitable for a wiring board for C) and various multilayer boards (dielectric layers, etc.).

[0002]

2. Description of the Related Art With the development of high-frequency devices applied to mobile communication such as mobile phones, MICs used therein are required to be small and have high performance. The following characteristics are required for such MIC wiring board materials. That is, first, (1) high relative permittivity (εr). This is because if the relative permittivity is high, the resonant circuit, the inductance, and the capacitor can be downsized at the operating frequency. (2) The quality factor Q (reciprocal of dielectric loss) must be high. This is because the loss can be reduced when the Q value is high. (3) The temperature coefficient of the relative permittivity and the temperature coefficient of the resonance frequency of the formed resonance circuit are small. In addition, (4) Conductor wiring can have a multilayer structure. Also, (5) the electrical resistance of the conductor is small. This is because if the electric resistance of this conductor is large, the Q value of the resonance circuit and the inductance will be small, and the transmission loss of the conductor line will be large.

Conventionally, as a material used for this type of substrate, for example, a BaO-TiO ₂ system or one in which a part of its constituent elements is replaced with another element (Japanese Patent Publication No. 58-20905),
A composition having a composite perovskite structure such as Ba (Mg _1/2 Ta _2/3 ) O ₃ (Japanese Patent Publication No. 59-23048), TiO ₂ -ZrO ₂ -SnO ₂
System or a part of its constituent elements replaced by another element (Japanese Patent Publication No. 54-35678), BaO-TiO ₂ -R ₂ O ₃ system (R:
Sintered bodies such as rare earth elements) (Japanese Patent Publication No. 56-226321) are known. However, although these materials have a large relative dielectric constant, when a conductor path is formed in a multilayer structure inside the wiring board, the firing temperature of the board is high, so only materials with high conductor resistance such as PT and Pd with a high melting point are used. Since it cannot be used, it is not possible to use a conductive material with a low melting point, such as Ag, Cu, or Au, which has a low conductor resistance. there were.

As conventional materials other than the above, low-priced ceramics such as alumina, steatite, or forsterite are known, but they have a large temperature coefficient, and if conductor paths are to be provided in a multilayer structure. However, for the same reason as above, there is a problem that only a conductor material having a large conductor resistance such as Pt, Pd, W and Mo can be used.

Further, in order to solve these problems, glass having a cordierite composition and TiO ₂ particles and R ₂ Ti ₂ O are used as a material which can be adjusted to have a large relative dielectric constant and a small temperature coefficient.
_{A material in which 7} particles (R: rare earth element) are dispersed and blended has been proposed (JP-A-4-83736). These materials have a large relative permittivity, and the above materials have a large relative permittivity and can be adjusted to have a small temperature coefficient. However, in terms of practicality such as reliability of the substrate and handling in manufacturing. There is a problem that desired mechanical properties are not sufficient.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and by incorporating novel acicular dielectric particles having excellent dielectric properties into a crystallized glass composition, Not only relative permittivity, quality factor, temperature coefficient,
Suitable for MIC wiring boards with improved mechanical properties,
It is an object of the present invention to provide a crystallized glass composition that can be fired at a low temperature.

[0007]

That is, the gist of the present invention is that crystallized glass is characterized in that needle-like dielectric particles having a relative dielectric constant of 15 or more and an aspect ratio of 3 or more are blended. It is a composition. The needle-shaped dielectric particles are characterized by blending barium, titanium and a rare earth element or an oxide containing titanium and a rare earth element as a main component. Further, the crystallized glass composition is a composition containing alumina, magnesia and silica as main components.

The present invention will be described in more detail below. The aspect ratio in the present invention is the ratio of the major axis of the acicular or columnar particles to the minor axis. The needle-shaped dielectric particles used in the present invention are not particularly limited as long as they have a relative permittivity of 15 or more and an aspect ratio of 3 or more.
Barium, titanium and rare earth elements or oxides containing titanium and rare earth elements as main components are preferable. Also,
The term "crystallized glass" as used in the present invention refers to a material composed of crystals and glass, but also includes glass in which all the starting materials are converted into crystals.

If the relative dielectric constant of the acicular dielectric particles is less than 15, the crystallized glass composition has a small relative dielectric constant, which is not preferable. On the other hand, if the aspect ratio is smaller than 3, the mechanical properties of the crystallized glass composition are not sufficient, which is not preferable.
The specific permittivity of the finally obtained crystallized glass composition varies depending on the application, and is preferably 6 or more, and the mechanical strength is preferably 200 MPa or more in terms of bending strength.

The crystallized glass composition of the first invention is 1200
It can be molded into a desired shape at a low temperature of ℃ or below, and it has dielectric properties such as relative permittivity, quality factor and temperature coefficient in the frequency band used, and electrical properties such as electrical insulation, as well as weather resistance and productivity. It is not particularly limited as long as it has good surface characteristics, but a composition containing alumina, magnesia and silica as the main components described in the third invention is preferable.

The point of the present invention is to compound needle-like dielectric particles having a relative permittivity of 15 or more and an aspect ratio of 3 or more with glass to form a composite, which has a high relative permittivity, a high relative permittivity and a high mechanical property. To obtain a crystallized glass composition having at the same time characteristic properties. Although the compounding ratio of the acicular dielectric particles in the crystallized glass composition is related to the desired dielectric properties and mechanical properties, it is preferably not more than 80% by volume. This is because if the content exceeds 80% by volume, the densification of the glass is hindered.

Further, as applied to general composite materials, in addition to acicular dielectric particles having a relative permittivity of 15 or more and an aspect ratio of 3 or more, they have mechanical characteristics or a mechanical property as a reinforcing material or a thermal expansion adjusting material. In order to adjust electric properties such as dielectric properties, a needle-like particle reinforcing material having a relative dielectric constant of less than 15 or a filler such as a particle shape or plate particles may be blended, if necessary. Examples of such fillers include titania, alumina, quartz, mullite, forsterite, quartz glass, silicon carbide, silicon nitride, aluminum borate and the like. Of these, titania has a large relative permittivity of about 100 and the temperature coefficient of the resonance frequency is about +450 ppm / ° C. By increasing the addition amount, the temperature coefficient can be adjusted to the positive side. Also, alumina, quartz,
Since mullite, forsterite, etc. do not have a large relative permittivity, it cannot be expected to improve the permittivity by adding them, but alumina can be expected to increase the strength, and quartz, mullite, forsterite, etc. adjust the thermal expansion coefficient. You can expect the effect of doing. Silicon carbide, silicon nitride, aluminum borate, etc. have a relative dielectric constant of 1 in the whisker form rather than in the particle form.
Mention may be made, as an example, of a needle-shaped particle reinforcing material having a number of less than 5. These acicular particles are materials used as a reinforcing material for general composite materials, and can be expected to have an effect of improving mechanical properties. The blending ratio of these fillers can be selected within a range where desired dielectric properties and mechanical properties are obtained.

When a wiring board is manufactured using the glass composition of the present invention, it is generally carried out as follows.
A green sheet is manufactured by applying a molding method such as a sheet molding method or an extrusion molding method from a mixed powder of raw materials of a crystallized glass composition in which needle-shaped dielectric particles and fillers and glass added as needed are mixed. , A conductive path having a predetermined pattern is formed by applying a printing method such as a screen printing method using a suitable conductive paste, and such green sheets are laminated and integrated, and the integrated one is baked. As a result, the intended wiring board can be obtained.

Next, the invention of the second invention will be described.
The rare earth element referred to in the second invention is La, as generally defined,
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
There are 17 kinds of elements, b, Lu and Y, Sc, and La, Ce, Pr, Nd, Pm, Sm, Eu, depending on the required characteristics of the dielectric material.
Gd, Tb and Dy are useful. The second invention is characterized by using acicular dielectric particles of barium, titanium and the above rare earth elements or oxides containing titanium and the above rare earth elements as main components, but additional components other than this main component Is not particularly limited, but Pb, Sr, Ca, Zr, Hf, B
One or more of i, Mn, Al, Mg, Si, Ge, Te, Ni, Tl, Sb, Co and Cr may be added, and the addition amount thereof is preferably 25% by weight or less in terms of oxide.

The composition ratio of barium, titanium and rare earth element is not particularly limited, but rare earth element
It is expressed as R and assuming +3 valence, the composition formula a ・ BaO ・ b ・ Ti
O ₂・ c ・ R ₂ O ₃ (In the formula, a, b, and c are molar ratios, and a + b + c = 1.
, 0.1 <a <0.2, 0.6 <b <0.8, 0.1 <c <0.2, R: rare earth element) is particularly preferable. The reason is that in high frequency bands such as the microwave band, the relative permittivity is as large as about 90 and the quality factor Q is as large as 1500 or more (dielectric loss is small). Furthermore, by adjusting the composition, the temperature coefficient τf of the resonance frequency is This is because it can be adjusted near 0.

The composition ratio of titanium and rare earth elements is not particularly limited, but specifically, R ₄ Ti ₉ O ₂₄ ,
R ₂ Ti ₄ O ₁₁ , R ₂ Ti ₃ O _9-x , R ₂ Ti ₂ O ₇ , RTiO ₃ , R ₂ TiO ₅ (R
Represents a rare earth element) and other compounds and solid solutions. The dielectric properties of these substances, such as relative permittivity εr, quality factor Q (reciprocal of dielectric loss tanδ) and temperature coefficient τf, depend on their crystal structure and composition, especially the type and composition ratio of rare earth elements, and manufacturing conditions. It varies greatly and is selected according to the purpose of use. For example, the dielectric property of R ₂ Ti ₂ O ₇ is
The r is about 35 to 45, the quality factor Q is about 500 to 12000, and the temperature factor τf is about 0 to -120, which varies depending on the type and composition ratio of rare earth elements and manufacturing conditions. The dielectric properties of R ₄ Ti ₉ O ₂₄ are as follows: relative permittivity εr of about 35, temperature coefficient τf of 0
There is about +80.

The method for producing dielectric needle particles of barium, titanium and rare earth elements or oxides containing titanium and rare earth elements as a main component of the second invention is a raw material containing barium, titanium and rare earth element components. Alternatively, a method of heat-treating a mixture of a raw material containing titanium and a rare earth element component and a melting agent may be mentioned. Hereinafter, this manufacturing method will be described.

Examples of barium raw materials include barium carbonate, oxides, hydroxides, chlorides, nitrates, sulfates and organic acid salts such as oxalates, formates and acetates. Those that become oxides and do not remain impurities are preferable. When the raw material is in powder form, the particle size is preferably small, specifically 5 μm or less, preferably 1 μm or less.

Examples of titanium raw materials include titanium oxides, hydroxides, oxyoxides, chlorides, nitrates, sulfates, oxalates, formates, acetates, alkoxides and other organic acid salts, and metals. However, it is preferable that the oxide becomes an oxide after heat treatment and no impurities remain. When the raw material is in powder form, the particle size is preferably small, specifically 5 μm or less, preferably 1 μm or less.

As a raw material for rare earth elements, oxides of rare earth elements are preferable, and salts such as carbonates are preferable.
Further, depending on the composition of interest, a raw material containing several kinds of rare earth elements such as a light rare earth oxide mixture obtained in the step of refining rare earth elements may be used. Alternatively, a metal may be used as a raw material. In any case, it is preferable that it becomes an oxide after heat treatment and no impurities remain. When the raw material is in powder form, the particle size is preferably fine, specifically 5
It is less than or equal to μm, preferably less than or equal to 1 μm.

The raw material of the additive component used when adding the additive component is not particularly limited, but simple substance, alloy, oxide, hydroxide, oxyoxide, chloride, nitrate, sulfate and oxalate salt, formate salt. Examples thereof include organic acid salts such as acetic acid salts and alkoxides, and mixtures thereof, and complex compounds composed of two or more kinds of components, but those that do not remain as impurities after heat treatment are preferable. When the raw material is in powder form, the particle size is preferably small, specifically 5 μm or less, preferably 1 μm or less.

As the raw material containing barium, titanium and rare earth element components or the raw material containing titanium and rare earth element components, a mixture of the above raw materials containing each component may be used, but further, each component is uniformly distributed. It is preferable that at least a part of titanium forms a complex compound and / or a solid solution. As a method for producing a raw material in which at least a part of these rare earth elements and titanium form a complex compound and / or a solid solution, there are a solid phase method, a liquid phase method such as a coprecipitation method, and a gas phase method. Although the method may be used, the solid phase method is preferable in terms of productivity and production efficiency.

The solid phase method is a method in which the raw materials of the above-mentioned constituents are mixed in a powder form and calcined. Mixing may be performed by a dry method or a wet method using a mixer, a ball mill, a vibration mill or the like, but the wet method is more efficient. The optimum calcination temperature varies depending on the composition, but it is 700 ℃ ~ 1500 ℃, preferably 900 ℃ ~
It is 1300 ° C. If the calcination temperature is less than 700 ° C, the solid-phase reaction of the mixed powder is insufficient, and if it exceeds 1500 ° C, strong agglomeration of the powders progresses and the powder becomes coarse and the powder characteristics deteriorate.
This is because the mixing characteristics with the melting agent deteriorate. Specific examples of the calcination method include calcination in an ordinary electric furnace or the like.

When the above-mentioned additional components are added in addition to the main component, a single compound of the additional components such as various salts such as oxides and carbonates of these additional components or a composite compound consisting of several additional components is used. It may be used in the form of powder or solution in the steps of the solid phase method, the liquid phase method, the gas phase method or the like, or may be added and mixed when mixed with the melting agent.

The melting agent is preferably one that melts under heat treatment conditions and does not cause a selective reaction with rare earth elements and titanium components, and sulfates and chlorides of alkali metals, glass phase forming components and the like are preferable. . Specific examples of alkali metal sulfates and chlorides include lithium sulfate, sodium sulfate, potassium sulfate, lithium chloride, sodium chloride,
Potassium chloride and hydrates thereof. Specific examples of the glass phase forming components, the boron compound include oxides of boron, for example, oxygen acid of boron oxide or boron, for example, orthoboric periodate (H ₃ BO _3), tetraborate (H ₂ B _Four
O ₇ ), metaboric acid (HBO ₂ ) or alkali metal salts thereof, such as sodium tetraborate, potassium tetraborate, sodium metaborate and boron alkoxide compounds,
For example, there are known salts such as boron ethoxide (B (OC ₂ H ₅ ) ₃ ). These melting agents may be used alone,
Moreover, you may mix 2 or more types.

If the amount of the melting agent added is small, the growth of the needle-shaped dielectric particles is hindered, and the needle-shaped dielectric particles are likely to aggregate with each other, and if too much is added, the post-treatment etc. becomes complicated. The effect of addition is small. Therefore, the optimum addition amount varies depending on the desired needle-shaped dielectric particle composition and the type of the melting agent used, but 25 to 500% by weight based on the weight of the raw material containing rare earth element and titanium component in terms of oxide. It is more preferably 50 to 300% by weight.

The method of mixing the raw material containing the main component and the melting agent is not particularly limited as long as it is a method capable of uniformly mixing, and any known dry method or wet method can be used. The dry type means mixing by a usual mixing method such as a mortar, a mixer and a ball mill. The wet method is a method of mixing a raw material containing a rare earth element and a titanium component with a melt raw material in a solution form.
When the wet method is used, it is preferable to add a drying step before the heat treatment.

The optimum heat treatment temperature of the mixture of the main component-containing raw material and the melting agent varies depending on the composition, but is 900 to 16
The temperature is 00 ° C, preferably 1000 to 1500 ° C. Heat treatment temperature is 9
If the temperature is lower than 00 ° C, the reaction for forming the acicular oxide dielectric material is not promoted, and if the temperature is higher than 1600 ° C, sticking of needle-shaped particles to each other and generation of an impurity phase are likely to occur, which is not preferable. Pt for heat treatment
A metal container that can be used at high temperatures, various ceramic containers, and the like can be used. It is preferable that these containers are hard to react with the raw material containing the main component and the melting agent. Also,
It is also possible to suppress the reaction with the container by heat-treating a mixture of the raw material containing the main component and the melting agent, which is molded by pressure molding or the like.

For the method of isolating the needle-shaped dielectric particles from the reaction product containing the melting agent, hot hydrochloric acid, hot sulfuric acid, hot nitric acid or a mixture thereof, hot caustic soda, hot water or the like may be used. A method of thoroughly washing with water after removing the water-soluble substance can be mentioned. When the glass phase is by-produced and it is difficult to remove it by the above method, it can be dissolved and removed by hydrothermal treatment with an acid or an alkali. When there is a water-insoluble by-product, the needle-shaped oxide dielectric particles may be separated from the residue by a treatment such as decantation and then washed sufficiently with water.

The crystallized glass composition containing alumina, magnesia and silica as the main components used in the third invention will be described below. Alumina, crystallized glass containing magnesia and silica as the main components in the present invention means that the crystal structure after firing is composed only of a cordierite crystal phase,
Or, if it is a composition containing glass or other crystals with the cordierite crystal phase as the main component, basically no problem occurs, and various known cordierite-based compositions containing alumina, magnesia and silica as the main components as the main components are used. A material containing glass or glass having a cordierite composition can be used. In the following description, the composition of both the main component and the additive component is expressed as an oxide and the ratio in terms of oxide is shown.
The use of an oxide as a raw material is not limited, and various salts of a metal that substantially becomes an oxide by heat treatment may be used as a raw material.

Specific examples of cordierite glass include:
SiO ₂ : 25 to 65% by weight, Al ₂ O ₃ : 10 to 45% by weight, MgO: 7
-25% by weight, B ₂ O ₃ : 0 to 20% by weight as a main component,
More preferably, SiO ₂ : 48-63% by weight, Al ₂ O ₃ : 10-25
Wt%, MgO: 10 to 25 wt%, B ₂ O _3: as a main component 4 to 10% by weight. 1100 ° C in these composition ranges
The firing and densification are possible even below. 65% SiO ₂
If it exceeds, the glass melting temperature rises, and crystallization rapidly progresses during sintering, so that the glass phase that aids sintering is insufficient and densification is hindered. Further, if the proportion of SiO ₂ is less than 25% by weight, the crystallization temperature rises and the temperature at which a dense sintered body can be obtained becomes high, which is not preferable. Al ₂ O ₃ ratio is 4
If it exceeds 5% by weight, the temperature at which a dense sintered body can be obtained becomes high, and if it is less than 10% by weight, the production of cordierite crystal phase is reduced, which is not preferable. If the proportion of MgO exceeds 25% by weight, the deformation during sintering becomes large, which is not preferable in practice. This is presumed to be due to the precipitation of magnesium silicate. Further, if the proportion of MgO is less than 7% by weight, there arises a problem that a dense sintered body cannot be obtained. If the proportion of B ₂ O ₃ exceeds 20% by weight, foaming tends to occur during sintering, the temperature range in which sintering is possible becomes narrow, and the strength and water resistance of the sintered body deteriorate.

In addition to the above main components, alkali metal oxides, oxides of alkaline earth metals such as CaO, BaO, and SrO, and metal oxides such as ZrO ₂ , ZnO, and PbO are added as necessary. It is added to improve sinterability. Also, M
Oxides of n, Cr, Fe, Co, Ni, Cu and rare earth metals are used for coloring purposes as needed. If necessary, a component such as TiO ₂ may be added as a nucleating agent for promoting crystallization. In addition to such additive components, some impurities may be mixed in during the glass manufacturing process or the like.

To prepare a glass of cordierite composition,
Various known vitrification techniques can be applied. The melting method generally used for producing glass is a method of melting a mixture in which each raw material component is mixed in a target cordierite composition ratio, and rapidly cooling the melt to obtain glass. The cordierite-based glass produced in this manner is used as glass powder when forming a molded sintered body such as a wiring board. In order to improve its moldability and sinterability, its particle size is Small size is desirable, particle size is generally 20μ
m or less, more preferably 10 μm or less.

The temperature coefficient of the resonance frequency of the cordierite glass is -80 to -40 ppm / ° C., and the mixing ratio of the dielectric needle particles and other fillers should be taken into consideration to obtain the desired characteristics. Is blended with. A glass composition in which various raw materials are mixed in a predetermined ratio is fired to densify a molded body formed by a method generally applied to cordierite glass, and further cordierite glass components are crystallized to form cordierite. A sintered body mainly composed of a crystal phase, dielectric needle particles, and a filler optionally added is manufactured. A firing temperature of 1100 ° C or lower can be applied, and the lower limit is about 800 ° C. Further, the crystallization of the cordierite glass component can be carried out simultaneously with or after the sintering step by keeping it at the firing temperature. The temperature range for crystallization is about 850-1100 ° C. As a sintering method, hot press or H applied which is applied at the time of sintering of general ceramics other than the normal pressure sintering.
A method such as IP may be applied. The main crystal phase produced by crystallization is cordierite, but depending on the glass composition, precipitation of a crystal phase of mullite, forsterite, spinel, etc., or retention of an amorphous phase may occur in addition to cordierite.

[0035]

In the present invention, since needle-shaped dielectric particles having an aspect ratio of 3 or more are blended, the needle-shaped particles in the sintered body have a different breaking energy and It acts as a dissipative source of fracture cracks and increases the energy required for fracture, which is considered to improve the strength of the sintered body. In addition, since the needle-shaped dielectric particles have a dielectric property with a relative dielectric constant of 15 or more, it is possible to achieve the desired dielectric property by adjusting the blending ratio at the same time. It is possible to exhibit excellent characteristics in which electrical characteristics such as the above are simultaneously improved.

[0036]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. [Preparation of acicular dielectric particles] To obtain the composition shown in Table 1.
BaCO ₃ powder (Sakai Chemical Co., Ltd.), TiO ₂ powder (Ishihara Sangyo Co., Ltd.)
And rare earth oxide powder (manufactured by Japan Yttrium Co., Sm ₂ O
₃ , Nd ₂ O ₃ ) was weighed, and then the needle-shaped dielectric particles were prepared by using potassium sulfate powder (K ₂ SO ₄ ) as a melting agent in a total amount of oxide-equivalent raw materials containing barium, titanium and rare earth element components. It was weighed so that the weight% shown in Table 1 was relative to the weight, and mixed by a ball mill for 10 hours. The obtained mixture was heat-treated at the temperature shown in Table 1 for 5 hours. The reaction product was cooled, added with an acid and boiled to remove the melting agent, and then thoroughly washed with water and dried. Table 1 shows the thickness, length, average value of aspect ratio, crystal phase identified by powder X-ray diffraction, and relative permittivity of the obtained acicular dielectric particles. The relative permittivity is
After crushing the obtained acicular particles, it is molded into a disk shape and the temperature is 1500.
After sintering at ˜1550, parallel polishing of the obtained sintered body, electrodes were formed on both sides of the disk, and the value at 1 MHz was measured. Hereinafter, the obtained dielectric needle particles are shown as needle particles 1 and needle particles 2 as shown in Table 1.

[Preparation of Powder] The raw material powder used in the above [Preparation of acicular dielectric particles] was weighed so as to have the composition shown in Table 1 and mixed by a ball mill for 10 hours. The obtained mixture was heat-treated at the temperature shown in Table 1 for 5 hours. The particle size of the powder obtained by grinding the heat-treated product with a ball mill for 10 hours (described in the column of "length" in Table 1), the crystal phase identified by powder X-ray diffraction, and the relative dielectric constant are shown in Table 1. It was The relative permittivity was measured under the same conditions as in the above [Preparation of acicular dielectric particles]. Hereinafter, the obtained powders are shown as powder 1 and powder 2 as shown in Table 1. As can be seen from Table 1, the acicular particles 1 and the powder 1 have the same composition, and the acicular particles and the powder having the same numbers have the same compositions.

[0038]

[Table 1]

[Preparation of Glass Composition Powder] Powder raw materials such as MgO, Al ₂ O ₃ , SiO ₂ and H ₃ BO ₃ were weighed and mixed in an automatic mortar for 20 minutes so as to have the composition shown in Table 2. did. The obtained mixture was heated to a temperature of about 1600 ° C. in a platinum crucible and melted, then dropped into water and rapidly cooled to obtain a glass composition. The obtained glass composition was pulverized with a ball mill for 20 hours to obtain a glass composition powder having a particle size of about 2 to 4 μm. Hereinafter, the obtained glass powder is shown as glass 1, glass 2, etc. as shown in Table 2.

[0040]

[Table 2]

[Examples 1 to 10 and Comparative Examples 1 to 10] The prepared acicular dielectric particles, powder and glass were weighed and mixed in the proportions shown in Table 3. The temperature of the resulting mixture is 900-1000 ° C.
It was baked for 1 hour. The obtained sintered body was cut and polished, and the three-point bending strength (according to JIS-R1601) was measured. The results are shown in Table 3. As is apparent from this, the mechanical properties of the crystallized glass composition (comparison between the numbers of the example and the numbers of the comparative examples) in which the acicular dielectric particles and the powders having the same composition were used in the same mixing ratio The strength is higher for the acicular dielectric particles, indicating that the mechanical properties of the glass composition can be improved by using the acicular dielectric particles.

[0042]

[Table 3]

[0043]

INDUSTRIAL APPLICABILITY According to the present invention, needle-like dielectric particles having a relative permittivity of 15 or more and an aspect ratio of 3 or more can be formed into a desired shape at a low temperature, and electrical characteristics such as dielectric characteristics in a frequency band used. Further, by combining with a glass composition having good manufacturing characteristics such as weather resistance and productivity, it is possible to exhibit excellent characteristics in which mechanical characteristics and electrical characteristics such as dielectric characteristics are simultaneously improved. , Especially high frequency integrated circuits (MI
The glass composition suitable for the wiring board for C) and various multilayer boards (dielectric layers, etc.) can be provided, and its industrial effect is great.

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[Procedure amendment]

[Submission date] September 22, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

Conventionally, as a material used for this type of substrate, for example, a BaO-TiO ₂ system or one in which a part of its constituent elements is replaced with another element (Japanese Patent Publication No. 58-20905),
A composition having a composite perovskite structure such as Ba (Mg _1/2 Ta _2/3 ) O ₃ (Japanese Patent Publication No. 59-23048), TiO ₂ -ZrO ₂ -SnO ₂
System or a part of its constituent elements replaced by another element (Japanese Patent Publication No. 54-35678), BaO-TiO ₂ -R ₂ O ₃ system (R:
Sintered bodies such as rare earth elements) (Japanese Patent Publication No. 56-226321) are known. However, although these materials have a large relative permittivity, when a conductor path is formed in a multilayer structure inside a wiring board, the firing temperature of the board is high, so only materials with high conductor resistance such as Pt and Pd with high melting points are used. Since it cannot be used, it is not possible to use a conductive material with a low melting point, such as Ag, Cu, or Au, which has a low conductor resistance. there were.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Further, in order to solve these problems, glass having a cordierite composition and TiO ₂ particles and R ₂ Ti ₂ O are used as a material which can be adjusted to have a large relative dielectric constant and a small temperature coefficient.
_{A material in which 7} particles (R: rare earth element) are dispersed and blended has been proposed (JP-A-4-83736). These materials have large dielectric constant, and the material has a large dielectric constant, and it is intended that the temperature coefficient can be reduced adjusted, in terms of handling of practical Men及 beauty during the production of the reliability and the like of the substrate desired is to have mechanical properties was a gutter cormorants problem not sufficient.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The present invention will be described in more detail below. The aspect ratio in the present invention is the ratio of the major axis of the acicular or columnar particles to the minor axis. The needle-shaped dielectric particles used in the present invention are not particularly limited as long as they have a relative permittivity of 15 or more and an aspect ratio of 3 or more.
Barium, titanium and rare earth elements or oxides containing titanium and rare earth elements as main components are preferable. Also,
The crystallized glass in the present invention refers to what is composed of a crystal and glass, but shall also include those glass as the starting material was converted to all crystals.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0012

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Further, as applied to general composite materials, in addition to acicular dielectric particles having a relative permittivity of 15 or more and an aspect ratio of 3 or more, they have mechanical characteristics or a mechanical property as a reinforcing material or a thermal expansion adjusting material. In order to adjust electric properties such as dielectric properties, a needle-like particle reinforcing material having a relative dielectric constant of less than 15 or a filler such as a particle shape or plate particles may be blended, if necessary. Examples of such fillers include titania, alumina, quartz, mullite, forsterite, quartz glass, silicon carbide, silicon nitride, aluminum borate and the like. Of these, titania has a large relative permittivity of about 100, and the temperature coefficient of the resonance frequency is about +450 ppm / ° C, and the temperature coefficient can be adjusted to the positive side by increasing the addition amount. Also, alumina, quartz,
Since mullite, forsterite, etc. do not have a large relative permittivity, it cannot be expected to improve the permittivity by adding them, but alumina can be expected to increase the strength, and quartz, mullite, forsterite, etc. adjust the thermal expansion coefficient. You can expect the effect of doing. Silicon carbide, silicon nitride, aluminum borate, etc. have a relative dielectric constant of 1 in the whisker form rather than in the particle form.
Mention may be made, as an example, of a needle-shaped particle reinforcing material having a number of less than 5. These acicular particles are materials used as a reinforcing material for general composite materials, and can be expected to have an effect of improving mechanical properties. The blending ratio of these fillers can be selected within a range where desired dielectric properties and mechanical properties are obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0014

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[0014] Next will be explained in the second of the inventions. The rare earth element referred to in the second invention is La, Ce, P as generally defined.
r, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
And 17 kinds of Y and Sc, depending on the characteristics of the required dielectric material, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb.
And Dy are useful. In the second invention, barium,
The needle-like dielectric particles of titanium and the rare earth element or an oxide containing titanium and the rare earth element as a main component are characteristic, but the addition component other than this main component is not particularly limited, but Pb , Sr, Ca, Zr, Hf, Bi, Mn,
One or more of Al, Mg, Si, Ge, Te, Ni, Tl, Sb, Co and Cr may be added, and the addition amount is usually 25 in terms of oxide.
It is preferably less than or equal to weight%.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

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The composition ratio of titanium and rare earth elements is not particularly limited, but specifically, R ₄ Ti ₉ O ₂₄ ,
R ₂ Ti ₄ O ₁₁ , R ₂ Ti ₃ O _9-x , R ₂ Ti ₂ O ₇ , RTiO ₃ , R ₂ TiO ₅ (R
Represents a rare earth element) and other compounds and solid solutions. The dielectric properties of these substances, such as relative permittivity εr, quality factor Q (reciprocal of dielectric loss tanδ) and temperature coefficient τf, depend on their crystal structure and composition, especially the type and composition ratio of rare earth elements, and manufacturing conditions. It varies greatly and is selected according to the purpose of use. For example, the dielectric property of R ₂ Ti ₂ O ₇ is
The r is about 35 to 45, the quality factor Q is about 500 to 12000, and the temperature factor τf is about 0 to -120, which varies depending on the type and composition ratio of rare earth elements and manufacturing conditions. The dielectric properties of R ₄ Ti ₉ O ₂₄ are as follows: relative permittivity εr of about 35, temperature coefficient τf of 0
It is about +80.

Claims (3)

[Claims] 1. A crystallized glass composition comprising acicular dielectric particles having a relative dielectric constant of 15 or more and an aspect ratio of 3 or more. 2. The crystallized glass composition according to claim 1, wherein the acicular particles are barium, titanium and rare earth elements, or oxides containing titanium and rare earth elements as main components. 3. The crystallized glass composition according to claim 1, wherein the crystallized glass contains magnesia, alumina and silica as main components.